TW202307057A - Reaction curable composition - Google Patents

Abstract

The present disclosure addresses the problem of providing a reaction curable composition that makes it possible to suppress reflection of light on the surface of a cured product by producing the cured product by curing the reaction curable composition. A reaction curable composition according to one aspect of the present disclosure contains a reactive component (A) and a filler (B). The filler (B) contains an antireflection filler (B1). The antireflection filler (B1) has an average particle diameter of 0.8-10 [mu]m, and the antireflection filler (B1) has a plurality of protrusions on the surface of particles thereof. The protrusions have an average diameter of 100-500 nm.

Description

reaction hardening composition

The present disclosure relates to a reaction hardenable composition, in particular to a reaction hardenable composition containing reactive ingredients and fillers.

Background technique

Patent Document 1 discloses a curable one-component epoxy resin composition comprising (a) an epoxy component comprising at least one epoxy compound having two or more groups per molecule, a latent hardener component, A thixotropy-imparting component, a polythiol component comprising a polythiol having at least one 2nd or 3rd thiol group per molecule, and a stabilizing component comprising a solid organic acid, and may also contain a pigment, if necessary, filler etc. Known technical literature

patent documents [Patent Document 1] Japanese Patent Application Publication No. 2014-500895

Summary of the invention

An object of the present disclosure is to provide a reaction-curable composition capable of suppressing light reflection on the surface of the cured product by curing it to produce a cured product.

A reaction-curable composition according to an aspect of the present disclosure contains a reactive component (A) and a filler (B). The aforementioned filler (B) contains an antireflection filler (B1). The average particle size of the aforementioned antireflective filler (B1) is not less than 0.8 μm and not more than 10 μm, and the aforementioned antireflective filler (B1) has a plurality of protrusions on the particle surface. The average diameter of the aforementioned protrusions is not less than 100 nm and not more than 500 nm.

form for carrying out the invention

First, the inventors will explain how the present disclosure was accomplished.

As adhesives, sealants, etc., reaction hardening compounds containing reactive components and fillers are used. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2014-500895) discloses a curable one-component epoxy resin composition containing (a) at least one ring compound having two or more groups per molecule. Epoxy components of oxygen compounds, latent hardener components, thixotropy-imparting components, polythiol components containing polythiols having at least one secondary or tertiary thiol group per molecule, and solid organic acids Stabilizing components, and pigments, fillers, etc. may also be included as needed.

The inventors focused on the use of adhesives in the manufacture of optical devices such as camera modules and the use of sealing materials as underfills, side fillers or coatings for optical components such as image sensors. In other cases, the adhesive and sealing material may cause noise due to regular reflection of light.

Then, the inventors studied the anti-glare method and the anti-reflection method as methods for suppressing regular reflection of light on the surface of a cured product obtained by curing the composition.

However, according to investigations by the inventors, it was found that the anti-glare method has the following problems.

(1) In the case of the anti-glare method using fillers, if only fine fillers or a combination of large particle size fillers and fine fillers are used to suppress the regular reflection of light, the composition will be easily thickened due to the filler. Especially in the absence of solvents, the amount of filler must be limited due to the suppression of excessive viscosification. Therefore, it is difficult to obtain a large reflection suppression effect. (2) In the anti-glare method using the phase separation method, it is very difficult to control the unevenness of the surface of the cured product. (3) In the anti-glare method using shape transfer, since post-processing of the hardened product is necessary, regular reflection of light cannot be suppressed only by hardening the composition, and especially in camera modules In the case of an adhesive, post-processing is difficult.

Also, according to investigations by the inventors, it was found that the anti-reflection method has the following problems.

(1) In the antireflection method using optical interference, since it is necessary to provide a laminated structure to the cured product, it becomes a complicated procedure, and it is difficult to apply this method particularly to an adhesive agent. (2) Anti-reflection method by lowering the refractive index of the cured product, especially obtained by curing a composition containing a reactive compound used in an adhesive such as an epoxy compound or an acrylic compound, or a sealing material The refractive index of the cured product is lower than about 1.4 at the lowest, and the refractive index difference with air will be large, so it is difficult to sufficiently suppress reflection. (3) In the anti-reflection method using pseudo-refractive index continuation, it is considered that roughness is formed on the surface of the hardened material by fine fillers with wavelengths below the visible light region, like a moth-eye structure. However, if only fine fillers or a combination of large particle size fillers and fine fillers are used to suppress the regular reflection of light, the composition will easily increase viscosity due to the filler. Especially in the absence of solvents, the amount of filler must be limited due to the suppression of excessive viscosification. Therefore, it is difficult to obtain a large reflection suppression effect.

Therefore, the inventors have worked hard to provide a reaction-curable composition that can produce a cured product by curing even without additional treatment such as post-processing, and suppress regular reflection of light on the surface of the cured product. research and development, so as to achieve the completion of this disclosure. However, the reasons for the completion of this disclosure should not limit the content of this disclosure. That is, for example, the application of the reaction-curable composition is not limited to adhesives and sealing materials, and is not limited to applications that must suppress regular reflection of light.

One embodiment of the present disclosure will be described below. In addition, the following embodiment is only one of various embodiment of this indication. As long as the purpose of this disclosure can be achieved, various changes can be made in the following embodiments according to the design.

The reaction-curable composition (hereinafter also referred to as composition (X)) of this embodiment contains a reactive component (A) and a filler (B). Filler (B) contains antireflective filler (B1). The average particle diameter of the antireflection filler (B1) is not less than 0.8 μm and not more than 10 μm. The antireflective filler (B1) has a plurality of protrusions on the particle surface thereof. The average diameter of the protrusions is not less than 100 nm and not more than 500 nm.

Furthermore, the antireflection filler (B1) may be a filler that satisfies the aforementioned particle size requirement and has the aforementioned protrusions. The name of the so-called anti-reflection filler (B1) is only set to distinguish the anti-reflection filler (B1) from other fillers (B2). The term "anti-reflection" in this name should not limit the anti-reflection filler ( The characteristics of B1).

According to this embodiment, a cured product can be obtained by reacting the reactive component (A) to harden the composition (X). The cured product contains anti-reflective filler (B1), and the anti-reflective filler (B1) tends to scatter light, thereby effectively suppressing regular reflection of light on the surface of the cured product. Therefore, in this embodiment, regular reflection of light on the surface of the cured product can be suppressed by producing the cured product from the composition (X).

Also, since the antireflection filler (B1) scatters light very easily, regular reflection of light on the surface of the cured product can be suppressed even if the amount of the filler (B) in the composition (X) is not too much. Therefore, the amount of the filler (B) in the composition (X) can be moderately suppressed, and the viscosity increase of the composition (X) due to the filler (B) can be suppressed. Therefore, for example, even if the composition (X) does not contain a solvent, or the composition (X) contains a small amount of solvent, the composition (X) can still have good fluidity.

In addition, by appropriately suppressing the amount of the filler (B) in the composition (X), it is also possible to achieve a low modulus of elasticity and a high elongation of the cured product. Thereby, the impact resistance of the cured product can be improved.

The composition (X) is a one-component type and is solvent-free, and its cured product preferably has sufficiently excellent antireflection performance against light having wavelengths in the visible region. The cured product of the composition (X) preferably still has sufficiently excellent antireflection performance for light having a wavelength in the near-infrared region (from 800 nm to 1000 nm). If the cured product has anti-reflection properties for light with wavelengths in the visible region, for example, when the composition (X) is used as an adhesive in a camera module, reflection of visible light in the camera module can be suppressed, thereby enabling Suppresses noise such as speckle noise in images output from image sensors, etc. In addition, if the cured product has anti-reflection performance for light having a wavelength in the near-infrared region, discoloration of an image output from an image sensor or the like can be suppressed. Therefore, it is particularly hoped that the light in the visible light region and the infrared light region will not be reflected in the internal optical path of the camera module or the like. In addition, the antireflection performance means the property which suppresses the regular reflection of light.

The details of the components of the composition (X) will be further described.

As mentioned above, in one embodiment of the present disclosure, the composition (X) contains the reactive component (A) and the filler (B). Filler (B) contains antireflective filler (B1). The average particle diameter of the antireflection filler (B1) is not less than 0.8 μm and not more than 10 μm. The antireflective filler (B1) preferably has protrusions with an average diameter of 100 nm to 500 nm in an area of 10% or more of the particle surface. The average diameter of protrusions is the average value of protrusion diameters. The protrusion diameter is the average value of the longitudinal diameter (the dimension of the long diameter) and the transverse diameter (the dimension in the direction perpendicular to the long diameter) of the protrusion.

The reactive component (A) refers to a component that reacts to polymerize. The reactive component (A) may contain, for example, a reactive compound (A1), or a reactive compound (A1) and a hardener (A2) that reacts with the reactive compound (A1).

The reactive compound (A1) may contain, for example, at least one of epoxy compounds and acrylic compounds.

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy compound contains, for example, at least one selected from the group consisting of: biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Bisphenol type epoxy resin; Hydrogenated bisphenol type epoxy resin such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin; epoxy resin containing naphthalene ring; Epoxy resins containing anthracyclines; cycloaliphatic epoxy resins; dicyclopentadiene epoxy resins; phenol novolac epoxy resins; cresol novolac epoxy resins; triphenylmethane epoxy resins ; Epoxy resins containing bromine; Aliphatic epoxy resins; Aliphatic polyether epoxy resins; Triglycidyl isocyanate; Silicone resins containing glycidyl groups; .

The epoxy compound preferably includes bisphenol epoxy resin, and more preferably includes at least one of bisphenol A epoxy resin and bisphenol F epoxy resin.

Acrylic compounds are compounds having at least one of acryl and methacryl groups in their molecules. The acrylic compound contains, for example, at least one selected from the group consisting of trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, dimethylol-tricyclodecane diacrylate ester, acrylmorpholine, tetrahydrofurfuryl acrylate, 4-hydroxybutyl acrylate, 9,9-bis(4-(2-(meth)acryloxyethoxy)phenyl)-9H -Treme, ginseng-(2-acryloxyethyl) isocyanate, bis-(2-acryloxyethyl) isocyanate, caprolactone modified ginseng-(2-acryloxyethyl) base) isocyanurate, isocyanate EO modified diacrylate and isocyanate EO modified triacrylate, etc.

The reactive compound (A1) is preferably liquid at 25°C. In this case, the thickening of the composition (X) can be further suppressed.

The compounds that can be included in the reactive compound (A1) are not limited to epoxy compounds and acrylic compounds. For example, the reactive compound (A1) may also contain a compound having an oxygen group in the molecule (oxygen compound), a compound having a vinyl group in the molecule (vinyl compound), and the like.

The case where the reactive component (A) contains the curing agent (A2) will be described.

The curing agent (A2) contains a compound that can react with the reactive compound (A1). The curing agent (A2) includes, for example, at least one selected from the group consisting of amine compounds, acid anhydrides, phenol compounds, thiol compounds, and imidazole compounds. The reactive compound (A1) preferably contains an epoxy compound, and the hardener (A2) preferably contains at least one selected from the group consisting of amine compounds, acid anhydrides, phenol compounds, thiol compounds and imidazole compound. The reactive compound (A1) preferably contains at least one of an epoxy compound and an acrylic compound, and the hardener (A2) preferably contains a thiol compound.

Amine compounds are compounds with amine groups in their molecules. The amine compound includes, for example, 4,4'-diamino-3,3'-diethyldiphenylmethane.

The acid anhydride contains, for example, one or more selected from the group consisting of: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, benzophenone tetracarboxylic anhydride, hexahydro-phthalic anhydride, Phthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and polyazelaic anhydride.

Phenolic compounds are compounds with phenolic hydroxyl groups in their molecules. The phenolic compound preferably has two or more phenolic hydroxyl groups in one molecule. The phenolic compound contains, for example, one or more selected from the group consisting of: phenol novolak resin, cresol novolak resin, biphenyl novolac resin, triphenylmethane type resin, naphthol novolak resin, phenol Aralkyl resins and biphenyl aralkyl resins.

Thiol compounds are compounds with thiol groups in their molecules. The thiol compound includes, for example, neopentylitol tetrakis(3-mercaptopropionate) (for example, Epomate QX40 manufactured by Mitsubishi Chemical Corporation) and the like.

The imidazole compound contains, for example, at least one selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl imidazole etc.

Furthermore, even when the reactive compound (A1) contains compounds other than epoxy compounds, the curing agent (A2) may contain an appropriate compound depending on the type of compound contained in the reactive compound (A1).

The content of the curing agent (A2) is, for example, 0.3 equivalents or more and 1.5 equivalents or less with respect to 1 equivalent of the reactive compound (A1).

The composition (X) may also contain a curing catalyst. At this time, by heating the composition (X), the hardening reaction of the composition (X) is facilitated. The hardening catalyst contains, for example, at least one component selected from the group consisting of imidazoles, cyclic amidines, tertiary amines, organic phosphines, tetrasubstituted phosphonium, tetrasubstituted borates, borates other than Quaternary phosphonium salts of counter anions, tetraphenyl boron salts, etc. The hardening catalyst may also contain a latent hardening catalyst. In this case, the reaction of the composition (X) in the unheated state can be suppressed, and the storage stability of the composition (X) can be improved. The latent hardening catalyst may contain at least one of a liquid latent hardening accelerator and a solid dispersion type latent hardening accelerator. The latent hardening catalyst may also contain a microcapsule type latent hardening catalyst. Microencapsulated latent hardening catalysts contain, for example, microencapsulated imidazoles comprising imidazoles as catalytically active compounds. The ratio of the curing catalyst is, for example, 0.1% to 20% with respect to the epoxy resin.

The composition (X) may also contain an initiator (C). Initiators (C) are compounds which initiate the reaction of the reactive components (A). For example, when the reactive component (A) contains an acrylic compound, the initiator (C) may contain a radical polymerization initiator. The radical polymerization initiator contains, for example, at least one compound selected from the group consisting of aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, sulfur compounds (thioxanthene Ketone compounds, compounds containing sulfur phenyl groups, etc.), hexaaryl bis-imidazole compounds, ketoxime ester compounds, borate compounds, azinium (azinium) compounds, metallocene compounds, active ester compounds, compounds with carbon-halogen bonds compounds and alkylamine compounds. The ratio of the initiator (C) is, for example, 0.1% by mass or more and 10% by mass or less with respect to the acrylic acid compound.

Examples of the combination of the reactive compound (A1) and the hardener (A2) or initiator (C) include a combination of an epoxy compound and an acid anhydride, a combination of an epoxy compound and an amine compound, an epoxy compound and a thiol Combination of compounds, combination of epoxy compound and phenolic compound, combination of epoxy compound, acrylic compound, thiol compound and initiator (C), and epoxy compound, acrylic compound, amine compound and initiator (C) combination. Furthermore, the combination of the reactive compound (A1) and the hardener (A2) or starter (C) is not limited to the aforementioned ones.

As mentioned above, the filler (B) is contained, and the filler (B) contains the antireflection filler (B1).

As described above, the average particle diameter of the antireflective filler (B1) is not less than 0.8 μm and not more than 10 μm. If the average particle diameter of the anti-reflective filler (B1) is more than 0.8 μm, the composition (X) will be difficult to thicken. If the average particle size is 10 μm or less, the fluidity of the composition (X) can be ensured when the composition (X) is permeated into a narrow gap and when it is discharged by a dispensing method. The average particle size is preferably at least 1 μm, more preferably at least 1.5 μm. In addition, the average particle size is preferably not more than 5 μm, more preferably not more than 4 μm. Furthermore, the average particle diameter is the median diameter calculated from the volume-based particle size distribution measured by the laser diffraction scattering method.

In addition, since the average diameter of the protrusions is not less than 100 nm and not more than 500 nm, visible light can be effectively scattered by the antireflection filler (B1), so that good antireflection performance can be imparted to the cured product.

Furthermore, the diameter of the protrusion is to photograph the particles of the anti-reflective filler (B1) by a differential scanning electron microscope, and measure the long diameter (longitudinal diameter) and the diameter perpendicular to the longitudinal diameter of the protrusions of the particles appearing in the obtained image. (transverse diameter), and then calculate the average value of the longitudinal diameter and transverse diameter. In addition, the mean diameter of the protrusions is an average value of the diameters of all the protrusions appearing in the image of 10 particles.

In order to more effectively scatter visible light, the average diameter of the protrusions of the anti-reflection filler (B1) is preferably greater than 200 nm. It is more preferable that this average diameter is 400 nm or more. The average diameter of the protrusions of the antireflective filler (B1) is preferably less than 500 nm. Also in the distribution of the protrusion diameters of the antireflective filler (B1), it is preferable that the frequency of 200 nm or more and 500 nm or less is relatively high. For example, the total number of protrusions with a protrusion diameter of 200 nm to 500 nm is preferably 50% or more of the total number of protrusions. Also, the frequency distribution curve of the projection diameter whose vertical axis is the number of projections and whose horizontal axis is the projection diameter preferably has a broad peak in the range of the projection diameter of 200 nm or more and 400 nm or less, and the broad peak has a uniformly high frequency . In this case, the protrusions of the antireflection filler (B1) can effectively scatter light in a wide wavelength region in the visible light region.

The anti-reflection filler (B1) preferably has protrusions in an area of 10% or more of the particle surface. In this case, the antireflection filler (B1) can impart better antireflection performance to the cured product. The particle surface in this case means the surface of the particle (hereinafter also referred to as base particle) when protrusions are removed from the particle of the antireflection filler (B1). The area of 10% or more of the surface of the particle has protrusions means that the particles of the anti-reflection filler (B1) have a shape in which a plurality of protrusions are attached to the surface of the base particle, and the area of the portion where the protrusions are attached to the surface of the base particle The ratio of the total (hereinafter also referred to as the adhesion area ratio) means 10% or more of the total surface area of the substrate particle. The adhesion area ratio is more preferably 20% or more, and more preferably 30% or more. Also, the adhesion area ratio is, for example, 100% or less, 95% or less, or 90% or less.

In addition, the adhesion area ratio was measured by differential scanning electron microscope photography, and the particle area and protrusion area were calculated from the obtained image.

The particles of the antireflection filler (B1) are core-shell particles having a core and a shell covering the core, and preferably have protrusions on the surface of the shell. That is, the base particle in the particles of the antireflection filler (B1) preferably has a core and a shell. At this time, due to the refractive index difference between the core and the shell, light can be scattered at the interface between the core and the shell. Therefore, the antireflection filler (B1) can more effectively scatter light.

The particles of the antireflection filler (B1) are preferably organic resin particles. Each of the core and the shell of the particles of the antireflective filler (B1) preferably comprises an organic resin. In these cases, the elastic modulus of the cured product of the composition (X) can be lowered, so the impact resistance of the cured product can be improved.

The particles of the anti-reflective filler (B1) contain at least one selected from the group consisting of, for example, acrylic resins such as PMMA (polymethyl methacrylate), silicone resins, styrene resins, melamine resins, and amine groups. Formate resin, etc. Also, when the particles of the antireflective filler (B1) are core-shell particles, each of the core and the shell contains, for example, at least one selected from the group consisting of: PMMA (polymethyl methacrylate), etc. Acrylic resin, silicone resin, styrene resin, melamine resin and urethane resin, etc.

When the particles of the antireflection filler (B1) are core-shell particles, for example, the core contains acrylic resin such as PMMA (polymethyl methacrylate), and each of the shell and protrusions contains silicone resin. In this case, the antireflection filler (B1) can more effectively scatter light, and the antireflection filler (B1) can further lower the modulus of elasticity of the cured product.

When the particles of the antireflection filler (B1) are core-shell particles, the core may also be a cavity. That is, the particles of the anti-reflection filler (B1) can also be hollow particles with a hollow shell and a shell covering the hollow.

Furthermore, the particles of the anti-reflective filler (B1) may not be core-shell particles. That is, the particles of the anti-reflective filler (B1) may also be homogeneous as a whole.

The refractive index of the particles of the anti-reflective filler (B1) preferably satisfies at least one of the following: below 1.7, and below the refractive index of the cured product of the reactive component (A). In this case, the total light reflectance (that is, the sum of the diffuse reflectance and the regular reflectance) of the cured product of the composition (X) can be maintained or reduced. The refractive index of the particles of the antireflective filler (B1) is more preferably 1.6 or less. The refractive index of the particles of the anti-reflection filler (B1) is preferably above 1.3.

Furthermore, the refractive index of the particles of the anti-reflection filler (B1) refers to the refractive index of the material of the particles when the particles of the anti-reflection filler (B1) are homogeneous as a whole, and when the particles of the anti-reflection filler (B1) are the core For shell-type particles, it is the refractive index of the shell. Furthermore, the refractive index of the core is also the same as that of the shell, and preferably satisfies at least one of the following: below 1.7, and below the refractive index of the cured product of the reactive component (A).

A commercial item can be used as an antireflection filler (B1). For example the antireflective filler (B1) may contain the trade name Silcrusta MKN03.

The filler (B) in the composition (X) may further contain a filler (B2) other than the antireflection filler (B1). If the average particle diameter of the filler (B2) other than the antireflective filler (B1) is more than 100nm and smaller than the average particle diameter of the antireflective filler (B1), the regular reflectance of the cured product of the composition (X) can be reduced. Furthermore, even if the particle size of the filler (B2) other than the antireflective filler (B1) is greater than the aforementioned range, as long as the filler (B2) is partially dissolved when the composition (X) is hardened, the filler (B2) in the hardened product ( If the particle size of B2) becomes smaller, the regular reflectance of the cured product of the composition (X) can be reduced by the filler (B2). As an example of the filler (B2) which can partially dissolve when the composition (X) hardens, powdery polyamine (for example, the product name EH-4357S manufactured by ADEKA Co., Ltd.) is mentioned. That is, even if the average particle diameter of the filler (B2) in the composition (X) is greater than the average particle diameter of the antireflection filler (B1), as long as the average particle diameter of the filler (B2) in the composition (X) is 100 nm or more And it is preferably smaller than the average particle size of the anti-reflection filler (B1). The average particle size of the filler (B2) in the cured product is more preferably at least 0.1 μm, and more preferably at least 0.2 μm. Moreover, it is more preferable that the average particle diameter of a filler (B2) is 3 micrometers or less, and it is still more preferable that it is 2 micrometers or less. The average particle size is the median diameter calculated from the volume-based particle size distribution measured by the laser diffraction scattering method. The filler (B2) can also be completely dissolved when the composition (X) hardens. At this time, once the filler (B2) is completely dissolved, the particles of the anti-reflection filler (B1) will be easily exposed on the surface of the hardened product, so the regular reflectance of the hardened product can be further reduced, and the particles of the filler (B1) It is also difficult to prevent the reduction of the total light reflectance of the cured product.

The particle shape of the filler (B2) is preferably a pulverized or angular shape. At this time, the regular reflectance of the cured product of the composition (X) can be further reduced by the filler (B2).

The filler (B2) may contain, for example, at least one of resin fillers and inorganic fillers.

The inorganic filler contains, for example, at least one selected from the group consisting of silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide , boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate and calcium zirconate, etc.

Resin fillers can improve the flexibility of hardened products. The resin filler contains, for example, at least one selected from the group consisting of silicone powder, polystyrene powder, acrylic resin powder, benzoguanamine resin powder, polybutadiene powder, etc., and includes the aforementioned two The powder of the above resins. Furthermore, the resins that the resin filler can contain are not limited to the aforementioned ones. The silicone powder contains, for example, at least one selected from the group consisting of: a powder composed of silicone rubber (silicone rubber powder), a powder composed of silicone resin (silicone resin powder), and Powder composed of a core of silicone rubber and a shell of silicone resin (silicone composite powder). In addition, the silicone resin refers to silicone having a skeleton mainly composed of 3-dimensional siloxane bonds, and the silicone rubber refers to silicone having a skeleton mainly composed of 2-dimensional siloxane bonds.

The inorganic filler hardens the composition (X), and hardening shrinkage in the process of producing a hardened product hardly occurs. Therefore, the composition (X) becomes more suitable for bonding parts in precision machines such as camera modules. The inorganic filler contains, for example, at least one selected from the group consisting of silica, alumina, barium sulfate, talc, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide , boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate and calcium zirconate, etc.

When the filler (B) contains a filler (B2) other than the antireflection filler (B1), it is preferable that the filler (B2) does not contain silica and alumina in order to lower the modulus of elasticity of the cured product of the composition (X). , or preferably the content of silica and alumina in the filler (B2) is low. Specifically, the ratio of silica and alumina to the composition (X) is preferably 10% by volume or less.

The ratio of the filler (B) including the antireflective filler (B1) to the composition (X) is preferably at least 10% by volume. At this time, once the composition (X) is hardened, the reaction of the reactive component (A) causes hardening shrinkage, and the particles 3 of the antireflective filler (B1) are exposed on the surface of the hardened product 1 (see FIG. 1 ). Therefore, the light scattering effect caused by the anti-reflection filler (B1) will be significantly generated, and the regular reflectance of the cured product can be further reduced. The ratio of the filler (B) is more preferably at least 20% by volume, and more preferably at least 25% by volume. Also, the ratio of the filler (B) is preferably at most 45% by volume. In this case, thickening due to the filler (B) of the composition (X) can be suppressed. This ratio is more preferably 40% by volume or less, and more preferably 35% by volume or less.

The amount of the antireflective filler (B1) is preferably not less than 5 parts by mass and not more than 82 parts by mass relative to 100 parts by mass of the reactive component (A). If the amount of the antireflection filler (B1) is more than 5 parts by mass, the regular reflectance of light on the surface of the cured product can be particularly reduced by the antireflection filler (B1). Also, if the amount of the antireflective filler (B1) is 82 parts by mass or less, thickening due to the antireflective filler (B1) of the composition (X) can be suppressed. The amount of the anti-reflective filler (B1) is more preferably at least 5 vol%, and more preferably at least 25 vol%. Moreover, this amount is more preferably 66 vol% or less, and more preferably 43 vol% or less.

The composition (X) preferably further contains a coloring material (D). At this time, since the light inside the cured product of the composition (X) is absorbed by the coloring material (D), the regular reflectance and total reflectance of the cured product can be further reduced.

The coloring material (D) preferably contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride and dyes. In this case, it is easier to reduce the regular reflectance and total light reflectance of the cured product. That is, since the transmittance of the cured product is lowered by the coloring material (D), light entering the cured product can be suppressed from being reflected at the interface of the member (adhered body, etc.) in contact with the cured product to escape to the outside.

The average transmittance of the cured product of the composition (X) in the wavelength range of 400nm to 800nm is preferably 10% or less, more preferably 1% or less. If the transmittance is less than 1%, the light that penetrates into the cured product, is reflected by the adherend, etc., and exits to the outside hardly affects the regular reflectance of the cured product.

When the composition (X) contains the coloring material (D), the amount of the coloring material (D) is preferably greater than 0 parts by mass and not more than 10 parts by mass relative to 100 parts by mass of the reactive component (A). The amount of the coloring material (D) is more preferably at least 0.1 parts by mass, and more preferably at least 0.3 parts by mass. Moreover, if the quantity of a coloring material (D) is 8 mass parts or less, it is more preferable, and it is still more preferable if it is 5 mass parts or less.

The composition (X) may further contain additives other than those described above within a range not excessively impairing the effects of the present embodiment. The additive contains, for example, at least one selected from the group consisting of: polymerization inhibitors, free radical scavengers, diluents, flexibility imparting agents, coupling agents, antioxidants, thixotropy imparting agents (thixotropy imparting agents ) and dispersants, etc.

The composition (X) preferably does not contain a solvent, or contains only a solvent inevitably mixed as a solvent. When the composition (X) contains a solvent, the ratio of the solvent to the composition (X) is preferably 0.1% by mass or less. In this case, the composition (X) can be suitably used as an adhesive, or suitably used to produce an underfill material. Also, in this embodiment, the antireflection performance of the cured product of the composition (X) can be improved while suppressing the thickening caused by the filler (B) of the composition (X), so the composition (X) The composition (X) does not contain a solvent or contains a small amount of solvent, and the composition (X) can have good fluidity, so the coating property and formability of the composition (X) can become good.

The viscosity of the composition (X) at 25°C measured with a B-type rotary viscometer at a rotation speed of 20 rpm is preferably below 200 Pa·s. In this case, the composition (X) can have particularly good applicability and formability. Also, as mentioned above, in this embodiment, since the thickening caused by the filler (B) of the composition (X) can be suppressed, and the antireflection performance of the cured product of the composition (X) can be improved, Therefore, the low viscosity of the aforementioned composition (X) can be realized. It is more preferable if the viscosity is below 100Pa·s, and even more preferable if it is below 50Pa·s. Also, this viscosity is, for example, 2 Pa·s or more.

Also, the viscosity of the composition (X) at 25°C measured with a B-type rotary viscometer at a rotation speed of 2 rpm is relative to the viscosity at 25°C measured with a B-type rotary viscometer at a rotation speed of 20 rpm The ratio (thixotropic index) (10rpm viscosity/100rpm viscosity) is preferably 1 or more and 7 or less. In this case, the composition (X) may have particularly good fluidity, and the composition (X) may be more suitably used as an adhesive, or more suitably used to make an underfill material. In particular, at this time, the composition (X) can be suitably used to produce an underfill material for an image sensor. In this embodiment, since the viscosity increase caused by the filler (B) of the composition (X) can be suppressed, and the antireflection performance of the cured product of the composition (X) can be improved at the same time, the aforementioned thixotropic index can be realized. . The thixotropic index is preferably at least 1.5, and more preferably at least 1.8. Furthermore, if the thixotropic index is below 5.0, it is better, and if it is below 4.0, it is even more preferable.

A cured product can be obtained by curing the composition (X). At this time, by an appropriate method corresponding to the composition of the reactive component (A) contained in the composition (X) and the composition of the initiator (C) and catalyst contained in the composition (X) as needed, the The reactive component (A) reacts to harden the composition (X). For example, the composition (X) can be hardened by heating. Also, when the composition (X) contains the initiator (C), the composition (X) can be cured by irradiating the composition (X) with light such as ultraviolet rays, and it is also possible to cure the composition (X) The composition (X) is cured by further heating after irradiation with light.

An outline of an example of a cured product 1 of the composition (X) is shown in FIG. 1 . Although the particles 3 of the anti-reflective filler (B2) are buried in the composition (X) before hardening, once the composition (X) hardens, hardening shrinkage caused by the reaction of the reactive component (A) will occur, so the antireflection Particles 3 of the reflective filler (B2) are exposed on the surface 2 of the cured product 1 . In the example shown in FIG. 1 , the particle 3 is a core-shell type particle having a core 32 and a shell 31 , and the particle 3 has a plurality of protrusions 33 on its surface. As mentioned above, the surface 2 of the hardened object 1 has fine unevenness due to the protrusions 33, so light diffuse reflection is easily generated on the surface 2 of the hardened object 1, and the total light reflectance of the surface 2 can also be reduced. itself. Therefore, the regular reflectance of light of the cured product 1 can be reduced. Also, as mentioned above, if the particle 3 is a core-shell type particle, due to the difference in refractive index between the core 32 and the shell 31, the diffuse reflection of light on the interface between the core 32 and the shell 31 is likely to occur, so it can be further improved. Reduce the regular reflectivity of light. Also, as mentioned above, if the average particle size of the anti-reflective filler (B1) is 0.8 μm or more, the composition (X) will be difficult to thicken, and if it is 10 μm or less, it can be used for the production of underfill materials, etc. The fluidity of the composition (X).

The average regular reflectance of the cured product of composition (X) measured at an incident angle of 8° using an integrating sphere for light with a wavelength of not less than 400 nm and not more than 800 nm is preferably not more than 0.5%, more preferably not more than 0.2%. The average regular reflectance of light with a wavelength of 800 nm to 1000 nm measured by the aforementioned method is preferably less than 0.5%, more preferably less than 0.2%. The average regular reflectance of light with a wavelength of 400nm or more and 1000nm or less measured by the aforementioned method is preferably less than 0.5%, more preferably less than 0.2%. In these cases, the regular reflection of light in the cured product can be particularly reduced. Therefore, when the cured product of the composition (X) is applied to an optical device, noise caused by light reflection in the cured product can be reduced. In this embodiment, such a low average regular reflectance can be realized. In addition, in order to reduce noise, the diffuse reflectance of the cured product of the composition (X) is preferably low.

The elastic modulus (storage elastic modulus) at -40°C of the cured product of the composition (X) is preferably 10 GPa or less. In this case, the cured product of the composition (X) tends to have good impact resistance, so the composition (X) can be used particularly suitably as an adhesive for camera modules. In addition, the elastic modulus at -40°C of 10 GPa or less means that the elastic modulus at or below the glass transition temperature of the cured product is low. In this embodiment, such a low modulus of elasticity of the cured product can be realized. The modulus of elasticity is more preferably below 6 GPa, and more preferably below 5 GPa. In addition, this modulus of elasticity is, for example, 1 GPa or more. Furthermore, the method of measuring the modulus of elasticity is described in the following examples.

As described above, the composition (X) is suitable, for example, as an adhesive, more specifically, for example, as an adhesive for bonding components of optical equipment such as a camera module to each other. In this case, even if the surface such as the end portion of the hardened product of the composition (X) to be bonded to each other is exposed to the outside, regular reflection of light on the surface can be suppressed. Therefore, in optical devices such as camera modules, the light reflected on the surface of the adhesive can be prevented from becoming a cause of noise. The material of the constituent parts bonded by the composition (X) may be, for example, resin materials such as liquid crystal polymers, polycarbonate, polyester, polyimide, metals such as nickel and copper, ceramics, glass, or other various substrate materials. etc., but not limited to. When using the composition (X) as an adhesive, for example, in a state where the composition (X) is located between two constituent parts, the composition (X) can be hardened by an appropriate method as described above, and the constituent parts can be follow each other.

As mentioned above, the composition (X) can also be suitably used to make an underfill material. The underfill material is a sealing material that seals the gap between a base material such as a printed wiring board and mounting components mounted on the base material. The composition (X) can be used particularly suitably when the mounting component is an optical element such as an image sensor. At this time, even if the surface such as the end of the underfill material is exposed to the outside, the regular reflection of light on this surface can still be suppressed, so it is possible to prevent the light regularly reflected on the surface of the underfill material from becoming a cause of noise in the optical element. . When producing an underfill material from the composition (X), for example, injecting the composition (X) into the gap between the base material and the mounting member mounted on the base material, it can be used in an appropriate manner as described above. The composition (X) hardens. (Summarize)

The reaction-hardenable composition concerning the 1st aspect of this disclosure contains a reactive component (A) and a filler (B). Filler (B) contains antireflective filler (B1). The average particle size of the antireflective filler (B1) is not less than 0.8 μm and not more than 10 μm, and the antireflective filler (B1) has a plurality of protrusions on the particle surface. The average diameter of the protrusions is not less than 100 nm and not more than 500 nm.

In this aspect, the reflection of light on the surface of the cured product can be suppressed by producing a cured product from a reaction-curable composition.

In the second aspect, in the first aspect, the antireflection filler (B1) has protrusions in an area of 10% or more of the particle surface.

In the 3rd aspect, in the 1st or 2nd aspect, a reactive component (A) contains a reactive compound (A1), and a reactive compound (A1) contains at least one of an epoxy compound and an acrylic compound.

In the fourth aspect, in the third aspect, the reactive component (A) further contains a curing agent (A2) that reacts with the reactive compound (A1).

A fifth aspect is the third or fourth aspect, further comprising an initiator (C).

The sixth aspect is that in any one of the first to fifth aspects, the refractive index of the anti-reflection filler (B1) satisfies at least one of the following: 1.7 or less, and the hardening of the reactive component (A) below the refractive index of the object.

The seventh aspect is that in any one of the first to sixth aspects, the particles of the anti-reflective filler (B1) are core-shell particles, which have a core and a shell covering the core, and have on the surface of the shell protrusion.

In the eighth aspect, in the seventh aspect, the core contains acrylic resin, and each of the shell and the protrusion contains silicone.

In a ninth aspect, in any one of the first to eighth aspects, the percentage of the filler (B) to the reaction-curable composition is 10% by volume or more.

In a tenth aspect, in any one of the first to ninth aspects, the amount of the antireflection filler (B1) is not less than 5 parts by mass and not more than 82 parts by mass relative to 100 parts by mass of the reactive component (A).

In an eleventh aspect, in any one of the first to tenth aspects, the reaction-curable composition further contains a coloring material (D).

In the twelfth aspect, the coloring material contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride, and dyes.

In a 13th aspect, in the 11th or 12th aspect, the amount of the coloring material (D) is greater than 0 parts by mass and 10 parts by mass or less with respect to 100 parts by mass of the reactive component (A).

The 14th aspect is the average regular reflection of light with a wavelength of 400nm or more and 800nm or less measured at an incident angle of 8° by the hardened product of the reaction-curable composition in any one of the 1st to 13th aspects. The rate is below 0.5%.

A fifteenth aspect is that in any one of the first to fourteenth aspects, the viscosity of the reaction-curable composition at 25°C measured with a B-type rotary viscometer at 20 rpm is 200 Pa·s or less.

The 16th aspect is that in any one of the 1st to 15th aspects, the viscosity of the reaction hardening composition at 25°C measured with a B-type rotary viscometer at 2 rpm is relative to the viscosity of the reaction-hardening composition measured with a B-type rotary viscometer The viscosity ratio (thixotropic index) at 25°C measured by the viscometer at 20 rpm is between 1 and 7.

A seventeenth aspect is any one of the first to sixteenth aspects, wherein the cured product of the reaction-curable composition has an elastic modulus at -40°C of 10 GPa or less.

In an eighteenth aspect, in any one of the first to seventeenth aspects, the reaction-curable composition does not contain a solvent, or contains only a solvent that is unavoidably mixed as a solvent.

A nineteenth aspect is any one of the first to eighteenth aspects, wherein the reaction hardening composition is an adhesive.

A 20th aspect is any one of the 1st to 18th aspects, wherein the reaction hardening composition is a composition used for making an underfill material. Example

The following is a more specific example of this embodiment. In addition, this embodiment is not limited only to the following examples. 1. Preparation of the composition

Compositions were prepared by mixing the raw materials shown in Table 1 to Table 4. Details of the raw materials shown in Tables 1 to 4 are as follows.

-YD8125: Liquid bisphenol A epoxy resin. Nippon Steel Chemical & Materials Co., Ltd., product name YD8125. Specific gravity 1.2.

-YDF8170: Liquid bisphenol F epoxy resin. Nippon Steel Chemical & Materials Co., Ltd., product name YDF8170. Specific gravity 1.2.

- #230: 1,6-Hexanediol diacrylate. Made by Osaka Organic Chemical Industry Co., Ltd. Product name Viscoat #230. The specific gravity is 1.02.

-MH-700: Liquid anhydride. Made by Nippon Chemical Co., Ltd., product name Rikacid MH-700. Specific gravity 1.2.

-EH-4357S: Polyamine in powder form. Made by ADEKA Co., Ltd., product name EH-4357S. Specific gravity 1.2.

-QX40: Liquid thiol compound. Manufactured by Mitsubishi Chemical Corporation. Neopentylthritol tetrakis(3-mercaptopropionate). The product name is Epomate QX40. The specific gravity is 1.26.

- MEH8000H: Liquid allylated phenol novolac resin. Made by Meihe Chemical Co., Ltd., product name MEH8000H. Specific gravity 1.2.

- Omnirad 184: 1-Hydroxycyclohexyl-phenyl ketone. IGM Resins B.V. product name Omnirad 184. Specific gravity 1.2.

-2P4MZ: 2-phenyl-4-methylimidazole. Shikoku Chemical Industry Co., Ltd. Specific gravity 1.1.

-HXA9322HP: microencapsulated imidazole. Made by Asahi Kasei E Materials Co., Ltd., product name Novacure HXA9322HP.

- Filler #1: core-shell type particles having protrusions on the particle surface, and having a core composed of polymethyl methacrylate and a shell composed of silicone resin. The average particle size is 3 μm. The protrusion diameter is 0.2~0.4μm. The average protrusion diameter is 0.3 μm. The attachment area ratio of protrusions is 60%. Made by Nikko RICA Co., Ltd., product name Silcrusta MKN03. Specific gravity 1.2.

- Filler #2: Spherical silica. The average particle size is 0.3 μm. Made by Admatechs, product name SC1053SQ. Specific gravity 2.2.

- Filler #3: Spherical silicone powder. Made by Nikko RICA Co., Ltd., product name MSP-SN08. The average particle size is 0.8 μm. Specific gravity 1.2.

- Filler #4: Silicone powder with protrusions on the surface. The average particle size is 4μm. The protrusion diameter is 0.1 μm or less. The average protrusion diameter is 0.1 μm or less. Made by Nikko RICA Co., Ltd., product name MSPTKN04. Specific gravity 1.2.

- Filler #5: Silicone powder with protrusions on the surface. The average particle size is 6μm. The protrusion diameter is 0.4 μm or more, and the average protrusion diameter is 0.6 μm. Made by Nikko RICA Co., Ltd., product name NHRASN06. Specific gravity 1.2.

- Filler #6: Spherical silica. The average particle size is 1.0 μm. Admatechs company make, product name SC4053SQ. Specific gravity 2.2.

-MA600MJ2: carbon black. The average particle size is 20nm. Mitsubishi Chemical Co., Ltd. product name MA600MJ2. Specific gravity 1.8.

-UF-8: titanium black. The average particle size is 20nm. Made by Mitsubishi Materials Corporation. Product name UF-8. Specific gravity 3.9. 2. Evaluation test

The following evaluation tests were performed on the aforementioned compositions. The results are shown in Tables 1 to 4. (1) Production of hardened products

A film having a size of 20 mm×50 mm×0.2 mm was produced by applying the composition on a slide glass.

In Examples 1-10 and Comparative Examples 15-20, the said film was heated and hardened, and the hardened|cured material was obtained. The temperature and time during heating are 120°C and 3 hours in Examples 1 and 2 and Comparative Examples 15-20, 80°C and 1 hour in Examples 3-8, and 120°C and 3 hours in Examples 9 and 10. Hour.

In Examples 11 and 12, a cured product was obtained by irradiating the above-mentioned film with ultraviolet rays and then heating and curing it. The irradiation conditions of ultraviolet rays are wavelength 365nm, illuminance 500mW/cm ² , and integrated light quantity 2000mJ/cm ² . The temperature and time during heating are 80°C and 1 hour.

In Examples 13 and 14, a cured product was obtained by irradiating the above-mentioned film with ultraviolet rays and curing it. The irradiation conditions of ultraviolet rays are wavelength 365nm, illuminance 500mW/cm ² , and integrated light quantity 2000mJ/cm ² . (2) Viscosity at 25°C

Using a B-type rotary viscometer (manufactured by Toki Sangyo Co., Ltd., model TVB-10), the viscosity of the composition at 25° C. was measured at a rotation speed of 20 rpm. (3) Thixotropic index at 25°C

Using a B-type rotary viscometer (manufactured by Toki Sangyo Co., Ltd., model TVB-10), the viscosity of the composition at 25° C. was measured at a rotation speed of 2 rpm. From this result and the viscosity obtained from the aforementioned "(1) Viscosity at 25°C", calculate the ratio of the viscosity at 25°C measured at a rotation speed of 20 rpm to the viscosity at 25°C measured at a rotation speed of 2 rpm (Thixotropic index) (2rpm viscosity/20rpm viscosity). (4) 400-800nm average positive reflectance

The cured product produced in the above "(1) Production of cured product" was used as a sample for evaluation, and the sample for evaluation was measured at an incident angle of 8° using a spectrophotometer UV-3600i Plus manufactured by Shimadzu Corporation. The total light reflectance, and the diffuse reflectance at an incident angle of 0°. The difference between the total light reflectance and the diffuse reflectance was calculated as the regular reflectance. From this result, the average value of the regular reflectance in the wavelength range of 400-800 nm was obtained, and it was made the average regular reflectance. (5) 800-1000nm average positive reflectance

The cured product produced in the above "(1) Production of cured product" was used as a sample for evaluation, and the sample for evaluation was measured at an incident angle of 8° using a spectrophotometer UV-3600i Plus manufactured by Shimadzu Corporation. The total light reflectance, and the diffuse reflectance at an incident angle of 0°, calculate the difference between the total light reflectance and the diffuse reflectance as the regular reflectance. From this result, the average value of the regular reflectance in the wavelength range of 800-1000 nm was obtained, and it was made the average regular reflectance. (6) 400-800nm average diffuse reflectance

The cured product produced in the above "(1) Preparation of cured product" was used as an evaluation sample, and the evaluation sample was measured at an incident angle of 0° using a spectrophotometer UV-3600i Plus manufactured by Shimadzu Corporation. The diffuse reflectivity. From this result, the average value of the diffuse reflectance in the wavelength range of 400-800nm was obtained, and it was made the average diffuse reflectance. (7) 800-1000nm average diffuse reflectance

The cured product produced in the above "(1) Preparation of cured product" was used as an evaluation sample, and the evaluation sample was measured at an incident angle of 0° using a spectrophotometer UV-3600i Plus manufactured by Shimadzu Corporation. The diffuse reflectivity. From this result, the average value of the diffuse reflectance in the wavelength range of 800-1000 nm was obtained, and it was made the average diffuse reflectance. (8) 400-1000nm average transmittance

The cured product produced in the above "(1) Preparation of cured product" was used as an evaluation sample, and the evaluation sample was measured at an incident angle of 0° using a spectrophotometer UV-3600i Plus manufactured by Shimadzu Corporation. The transmittance of light. From the results, the average value of the transmittance in the range of wavelength 400-1000nm was obtained, and it was made the average transmittance. (9) Adherence

Adhesive force when the composition was used as an adhesive was measured by the following method. The composition was coated on a glass substrate to prepare a coating film with a diameter of 3 mm and a thickness of 0.5 mm. This coating film was cured under the same conditions as in the case of the aforementioned "(1) Preparation of cured product" to obtain a cured product. The shear bonding strength of the cured product to the bonded body was measured by a shear testing machine.

Based on this result, the adhesive force was evaluated on the basis of the following criteria. A: More than 15MPa. B: 5 MPa or more and less than 15 MPa. C: Less than 5 MPa. (10) modulus of elasticity

A release film made of polyethylene terephthalate was placed on the glass plate, and a spacer made of silicone having a space of 3 mm×50 mm in plan view and 0.5 mm in thickness was placed on the release film. After the composition was flowed into the inner space of the spacer, a release film made of polyethylene terephthalate was placed on the upper surface of the spacer, and a glass plate was placed on the release film. Next, the composition was cured under the same conditions as in the case of the aforementioned "(1) Preparation of cured product" to prepare a sample for evaluation.

Using a viscoelasticity measuring device DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd., the sample for evaluation was measured under the conditions of frequency frequency: 1 Hz, measurement mode: tensile, and the storage elastic modulus at -40°C was measured as follows. Benchmarks are assessed. A: 1 GPa or more and less than 4 GPa. B: 4 GPa or more and less than 7 GPa. C: 7 GPa or more. [Table 1] Example 1 2 3 4 5 6 7 Reactive compounds (parts by mass) YD8125 twenty one twenty one 33 33 33 twenty one twenty one YDF8170 twenty one twenty one 33 33 33 twenty one twenty one #230 Hardener (parts by mass) MH-700 57 57 EH-4357S 11 11 11 QX40 32 32 MEH8000H Initiator (parts by mass) OMNIRAD 184 Catalyst (parts by mass) 2P4MZ 1 1 HXA9322HP twenty three twenty three twenty three 26 26 Filler (parts by mass) Filler #1 43 66 5 25 66 5 25 Filler #2 Filler #3 Filler #4 Filler #5 Filler #6 Pigment (parts by mass) MA600MJ2 1 1 1 1 1 1 1 UF-8 Total volume ratio of anti-reflective filler 30% 40% 5% 20% 40% 5% 20% The volume ratio of the total filler 30% 40% twenty three% 35% 51% 13% 27% assessment Viscosity at 25°C (Pa・s) 7 35 3 7 150 3 15 Thixotropic index 1.5 2.0 1.9 2.1 2.6 1.1 1.2 400-800nm average regular reflectance (%) <0.2 <0.2 0.3 <0.2 <0.2 0.3 <0.2 800-1000nm average regular reflectance (%) <0.2 <0.2 0.45 <0.2 <0.2 0.45 <0.2 400-800nm average diffuse reflectance (%) 4.7 3.2 5.5 4.5 3.8 5.7 4.5 800-1000nm average diffuse reflectance (%) 4.6 3.1 5.5 4.4 3.7 5.7 4.4 400-1000nm average transmittance (%) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Adhesion force (MPa) A B A A B A A Elastic modulus (GPa) B B B B B A B [Table 2] Example 8 9 10 11 12 13 14 Reactive compounds (parts by mass) YD8125 twenty one 27 27 17 17 YDF8170 twenty one 27 27 17 17 #230 19 19 51.8 51.8 Hardener (parts by mass) MH-700 EH-4357S QX40 32 38.8 38.8 47.6 47.6 MEH8000H 45 45 Initiator (parts by mass) OMNIRAD 184 1.2 1.2 0.6 0.6 Catalyst (parts by mass) 2P4MZ 1 1 HXA9322HP 26 7 7 Filler (parts by mass) Filler #1 66 43 66 43 66 43 82 Filler #2 Filler #3 Filler #4 Filler #5 Filler #6 Pigment (parts by mass) MA600MJ2 1 1 1 UF-8 1 1 1 1 Total volume ratio of anti-reflective filler 40% 30% 40% 30% 40% 30% 45% The volume ratio of the total filler 45% 30% 40% 32% 41% 30% 45% assessment Viscosity at 25°C (Pa・s) 50 15 50 5 120 3 10 Thixotropic index 1.5 1.2 1.5 1.6 2.1 2.9 4.5 400-800nm average regular reflectance (%) <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 800-1000nm average regular reflectance (%) <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 400-800nm average diffuse reflectance (%) 3.3 5.1 3.5 5 4.2 3.5 2.4 800-1000nm average diffuse reflectance (%) 3.2 5 3.4 5 4.1 3.5 2.4 400-1000nm average transmittance (%) <0.1 <0.1 <0.1 2 2 2 2 Adhesion force (MPa) B A B A A B B Elastic modulus (GPa) B B B A A A A [table 3] comparative example 15 16 17 18 19 20 Reactive compounds (parts by mass) YD8125 twenty one twenty one twenty one twenty one twenty one twenty one YDF8170 twenty one twenty one twenty one twenty one twenty one twenty one #230 Hardener (parts by mass) MH-700 57 57 57 57 57 57 EH-4357S QX40 MEH8000H Initiator (parts by mass) OMNIRAD 184 Catalyst (parts by mass) 2P4MZ 1 1 1 1 1 1 HXA9322HP Filler (parts by mass) Filler #1 0 Filler #2 79 Filler #3 43 Filler #4 43 Filler #5 43 Filler #6 79 Pigment (parts by mass) MA600MJ2 1 1 1 1 1 1 UF-8 Total volume ratio of anti-reflective filler 0% 0% 0% 0% 0% 0% The volume ratio of the total filler 0% 30% 30% 30% 30% 55% assessment Viscosity at 25°C (Pa・s) 3 250 20 9 6 16 Thixotropic index 2.1 1.8 1.3 1.7 1.5 1.3 400-800nm average regular reflectance (%) 3.6 2.6 2.5 2.2 1.7 2.6 800-1000nm average regular reflectance (%) 3.8 2.9 2.8 2.5 2 2.9 400-800nm average diffuse reflectance (%) 3.1 3.4 3.5 3.8 4.3 3.4 800-1000nm average diffuse reflectance (%) 3.1 3.2 3.5 4 3.1 400-1000nm average transmittance (%) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Adhesion force (MPa) A B B B B B Elastic modulus (GPa) B C B B B C 3. Additional evaluation (1) Evaluation of the protrusion of packing #1

The particles of the aforementioned filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03) were photographed using a differential scanning electron microscope to obtain an image. The image is shown in FIG. 7 . As shown in FIG. 7, the particles of filler #1 have protrusions on the entire surface. Measure the longitudinal diameter (the dimension of the long diameter) and the transverse diameter (the dimension perpendicular to the long diameter) of the protrusions from the image for 10 particles (the total number of protrusions is more than 100), and calculate the average of the longitudinal and transverse diameters The value is used as the diameter of the protrusion.

The results are shown in the graph of FIG. 2 . In this graph, the horizontal axis represents the diameter of the protrusions, and the vertical axis represents the frequency (the number of protrusions), respectively. As shown by this result, the frequency of the protrusion diameter of filler #1 is uniformly high in the range of 200 nm to 500 nm. (2) Comparative evaluation of fillers

A mixture having the composition of Example 1 except that the filler was not contained, and the aforementioned filler #1 were mixed so that the ratio of the filler #1 became 40% by mass to prepare a composition. Also, filler #3 (manufactured by Nikko RICA Co., Ltd., product name MSP-SN08), filler #4 (manufactured by Nikko RICA Co., Ltd., product name MSPTKN04), and filler #5 (manufactured by Nikko RICA Co., Ltd., product name NHRASN06) were used. Each was used instead of Filler #1, and the composition was prepared in the same manner.

Each composition was coated on a glass slide with a spatula, and then hardened by heating at 120° C. for 3 hours to produce a film-like cured product with a thickness of 0.2 μm. Visually confirming the appearance of the cured product in the case of using filler #1, it was found that the surface gloss was lower than that of other cured products.

Also, the average regular reflectance of the surface of each cured product was measured by the same method as in "(4) 400-800nm average regular reflectance" of the aforementioned "2. Evaluation test". As a result, the average regular reflectance in the case of using filler #3 was 2.53%, the average regular reflectance in the case of using filler #4 was 2.18%, and the average regular reflectance in the case of using filler #5 was 1.70%, The average regular reflectance with Filler #1 was significantly lower at 0.14%. (3) Evaluation of filler blending amount

In addition to changing the ratio of filler #1 in the composition to 0% by volume, 10% by volume, 20% by volume, 30% by volume, 32% by volume and 35% by volume, the preparation was compared with the aforementioned "(2) Filler "Assessment" situation of the same composition.

Using each composition, it carried out similarly to the case of said "(2) Filler comparison evaluation", and produced the hardened|filmed material.

Measure the regular reflection on the surface of each cured product in the same way as the above-mentioned "(4) 400-800nm average regular reflectance" and "(6) 400-800nm average diffuse reflectance" in the aforementioned "2. Evaluation test" Ratio spectrum and diffuse reflectance spectrum. Also, for each cured product, the total light reflectance spectrum was obtained from the regular reflectance spectrum and the diffuse reflectance spectrum. The regular reflectance spectrum is shown in FIG. 3 , the diffuse reflectance spectrum is shown in FIG. 4 , and the total light reflectance spectrum is shown in FIG. 5 .

As shown in this result, the higher the ratio of filler #1 becomes, the lower the regular reflectance becomes, especially when the ratio of filler #1 changes from 20% by volume to 30% by volume, the regular reflectance becomes extremely low. Also, the higher the ratio of filler #1, the higher the diffuse reflectance tends to be. In particular, when the ratio of filler #1 is changed from 20% by volume to 30% by volume, the diffuse reflectance becomes extremely high. Filler #1 The ratio of 1 becomes higher. This is presumed to be because when the ratio of filler #1 becomes 30% by volume, the particles of filler #1 are exposed to the outside on the surface of the cured product, so the diffusion of light by filler #1 increases dramatically. Also, the total light reflectance becomes lower as the ratio of filler #1 becomes higher. (4) Surface image of hardened material

In the aforementioned "(3) Evaluation of filler blending amount", when the ratio of filler #1 in the composition is 30% by volume, the image obtained by photographing the surface of the hardened product using a differential scanning electron microscope is shown in Figure 6. From this, it can be confirmed that when the ratio of filler #1 is 30% by volume, the particles of filler #1 are exposed on the surface of the cured product.

1: Hardened 2: surface 3: Particles 31: shell 32: nuclear 33:Protrusion

[ Fig. 1] Fig. 1 is a schematic cross-sectional view of an example of a hardened product of a reaction-curable composition in an embodiment of the present disclosure.

[ Fig. 2] Fig. 2 is a graph showing the frequency of protrusion diameters of particles of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03).

[ Fig. 3] Fig. 3 is a graph showing regular reflectance spectra for each of cured products of a plurality of compositions having different concentrations of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03).

[ Fig. 4] Fig. 4 is a graph showing the diffuse reflectance spectrum of each of cured products of a plurality of compositions having different concentrations of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03).

[ Fig. 5] Fig. 5 is a graph showing the total light reflectance spectrum of each of cured products of a plurality of compositions having different concentrations of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03).

[ Fig. 6 ] Fig. 6 is an image obtained by using a differential scanning electron microscope to photograph the surface of the cured product of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03) with a concentration of 30% by volume.

[ Fig. 7] Fig. 7 is an image obtained by photographing particles of filler #1 (manufactured by Nikko RICA Co., Ltd., product name Silcrusta MKN03) using a differential scanning electron microscope.

1: Hardened

2: surface

3: Particles

31: shell

32: nuclear

33:Protrusion

Claims (20)

A reaction-curable composition comprising a reactive component (A) and a filler (B), The aforementioned filler (B) contains an antireflection filler (B1), The average particle size of the aforementioned antireflective filler (B1) is not less than 0.8 μm and not more than 10 μm, and the aforementioned antireflective filler (B1) has a plurality of protrusions on the particle surface, The average diameter of the aforementioned protrusions is not less than 100 nm and not more than 500 nm. The reaction hardening composition according to claim 1, wherein the anti-reflection filler (B1) has the protrusions on an area of 10% or more of the particle surface. The reaction hardening composition according to claim 1 or 2, wherein the reactive component (A) contains a reactive compound (A1), and the reactive compound (A1) contains at least one of an epoxy compound and an acrylic compound. The reaction-curable composition according to claim 3, wherein the reactive component (A) further contains a curing agent (A2) that reacts with the reactive compound (A1). The reaction-curable composition according to claim 3, which further contains an initiator (C). The reaction hardening composition according to claim 1 or 2, wherein the refractive index of the aforementioned antireflective filler (B1) satisfies at least one of the following: below 1.7, and the refractive index of the hardened product of the aforementioned reactive component (A) below the rate. The reaction hardening composition according to Claim 1 or 2, wherein the particles of the aforementioned antireflective filler (B1) are core-shell particles having a core and a shell covering the core, and having the aforementioned protrusions on the surface of the aforementioned shell . The reaction-curable composition according to claim 7, wherein the core contains acrylic resin, and each of the shell and the protrusion contains silicone. The reaction-hardening composition according to claim 1 or 2, wherein the percentage of the aforementioned filler (B) relative to the aforementioned reaction-hardening composition is 10% by volume or more. The reaction curable composition according to claim 1 or 2, wherein the amount of the antireflective filler (B1) is 5 parts by mass to 82 parts by mass relative to 100 parts by mass of the reactive component (A). The reaction-curable composition according to claim 1 or 2, which further contains a coloring material (D). The reaction hardening composition according to claim 11, wherein the coloring material contains at least one selected from the group consisting of carbon black, titanium black, zirconium nitride and dyes. The reaction-curable composition according to claim 11, wherein the amount of the coloring material (D) relative to 100 parts by mass of the reactive component (A) is greater than 0 parts by mass and not more than 10 parts by mass. The reaction-curable composition according to claim 1 or 2, wherein the hardened product of the above-mentioned reaction-curable composition has an average regular reflectance of 0.5% for light with a wavelength of more than 400nm and less than 800nm measured at an incident angle of 8° using an integrating sphere the following. The reaction hardening composition according to claim 1 or 2, whose viscosity at 25°C measured with a B-type rotary viscometer at 20 rpm is below 200 Pa·s. For the reaction hardening composition of claim 1 or 2, the viscosity at 25°C measured with a B-type rotary viscometer at 2 rpm is relative to the viscosity at 25°C measured at 20 rpm with a B-type rotary viscometer The ratio of viscosity, that is, the thixotropic index, is above 1 and below 7. The reaction-curable composition according to claim 1 or 2, wherein the elastic modulus of the hardened product of the reaction-curable composition at -40°C is 10 GPa or less. The reaction-curable composition according to claim 1 or 2 does not contain a solvent, or contains only a solvent that is inevitably mixed as a solvent. The reaction hardening composition according to claim 1 or 2, which is an adhesive. The reaction hardening composition according to claim 1 or 2, which is a composition used for making underfill materials.

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